Black disazo dye.



UNITED STATES FFICE.

AT NT PAUL JULIUS, OF LUDIVIGSI'IAFEN, GERMANY, ASSIGNOR TO THEBADISCI'IE ANILIN AND SODA FABRIK, OF SAME PLACE.

BLACK DISAZO DYE.

SPECIFICATION forming part of Letters Patent N0. 644,239, dated February2'7, 1900.

Application filed February 18, 1899. Serial No. 706051. ($pecimens.)

To all whom it may concern.-

Be it known that I, PAUL JULIUS, doctor of philosophy, a subject of theEmperor of Austria-Hungary, residing at Ludwigshafen-onthe-Rhine, in theKingdom of Bavaria and Empire of Germany, have invented new and usefulImprovements in the Manufacture of Disazo Dyes from OhloramidophenolSulfo- Acid, (for which patents have been obtained in Germany, No. B.23,287, dated August 27, 1898; in England, No. 25,650, dated December 5,1898, and in France, No. 271,265, dated November 25, 1898,) of which thefollowing is a specification.

My invention relates to disazo coloring-matters which can be obtainedfrom ortho-ch1orortho-amido-phenol-para-sulfo-acid employing as middlecomponent either alpha-naphthylamin or the alpha-naphthylamin-6- or 7sulfo acids, known as Cleves, either mixed with one another or not, andas end components the alpha-naphthol-et-sulfo-acid,beta-naphthol-3.6-disulfo-acid, (R-salt,) thealpha-naphthol-fi-sulfo-acid, and when the Cleves sulfo-acids ofalpha-naphthylamin are used as middle component alpha-naphthylamin orR-salt can be well used as end components; but although I mention theseinstances of end components as being well suited for use in theinvention myinvention is not limited to their use; but other azo-dyecompo:

nents which are in practical use as end components in the manufacture ofazo dyes can also, if desired, be used in accordance with thisinvention.

In the present application for Letters Patent I desire to claimgenerically the new coloring-matters, being the disazo dyesoforthochlor-orthoamido-phenol-para-sulfo-acid, and specifically I claimthat coloring-matter of this new class which contains alphanaphthyl aminas middle component and beta-naphthol 3.6-disulfoacid (R-salt) as endcomponent.

The ortho-chlor-ortho-amido-phenol-parasulfo-acid which I use as myinitial material can be prepared from the correspondingnitroamido-sulfo-acid. For this purpose the said nitro-amido-acid isdiazotized and the diazo compound treated, according to Gattermannsprocess,with finely-divided copper,which can be prepared according tothe method de ing directions for the production of this orthochlor orthoamido phenol para-sulfo-acid: Dissolve about two hundred and thirty-fourparts of the ortho-nitro-ortho-amido-phenolpara-sulfo acid in onethousand parts of water, to which two hundred and thirty parts ofcaustic-soda lye (containing about thirty-five per cent. Na.O.H.) havebeen added. To this solution add a concentrated aqueous solution ofseventy parts of sodium nitrite. Allow the whole mixture to run into amixture of four hundred parts of hydrochloric acid (containing aboutthirty per cent. real H.Ol) diluted with five hundred parts of .water.Add to the diazo solution thus obtained six hundred parts ofhydrochloric acid (containing about thirty per cent. real H.Cl) andfifty parts of copper in the -finely-divided state known as molecularcopper. The copper is preferably added in the form of a fifty-percent.paste. Keep the mixture cool with ice during this addition, so that thetemperature at no time rises above 15 centigrade. When no diazo compoundis present in the solution, filter and precipitate thechlor-nitro-phenolsulfo-acid resulting by the addition of about fourhundred parts of potassium chlorid. Reduce in any ordinary way-forinstance, with iron filings and acetic acid. Render the product alkalinewith carbonate of soda, filter from the iron mud, concentrate thefiltrate, if necessary, and precipitate thechlor-amidophenol-sulfo-acidwithhydrochloricacid. Purify, it necessary,by redissolving and recrystallizing.

The following example will serve to illustrate the manner in which myinvention is best carried into practical effect and a disazo dyeof thenew class obtained:

Example: Production of the new intermediate coloring-matter fromoriho-chlor-orthoam ido-p henoZ-p arctsulfo-acid andalphamaphthylamc'n.-Stir to a paste one hundred and twelve parts of thechlor-amido-phenol-sulfoacid and five hundred parts of water. Add

about sixty parts of caustic-soda lye, (containing about thirty-five percent. Na.O.I-I.,) so as to dissolve the acid. To the solution add fivehundred parts of ice-water and one hundred and fifty-five parts ofhydrochloric acid, (containing about thirty per cent. real H. Cl.) Stirand add a concentrated solution of thirty-five parts of sodium nitritein order to diazotize. Run the diazo solution into a solution of abouteighty parts of alpha-naphthylamin in ninetyfive parts of hydrochloricacid (containing about thirty per cent. real 11.01) diluted with twothousand five hundred parts of Water. Heat the mixture forabout-thirty-six hours to a temperature of from to centigrade. When nofurther diazo compound can be ascertained by tests to be present in theliquid, allow the mixture to cool. Filter, press, and dry, or preferablypreserve this intermediate coloring-matter in the form of paste forfurther use. The coloring-matter so obtained is a dark-green powder,which is but slightly soluble in water, but soluble in alkalies with ared color. In a similar manner intermediate coloring-matter from Glevesacid can be obtained. This coloring-matter is more soluble, owing to thepresence of an extra sulfo group; but in other respects it closelyresembles the intermediate coloring-matter from naphthylamin.

Production of the new ohsazo coloring-matterfrom the intermediatecolortngwnatterfiom ortho chlor ortho-avnido-phenolware sulfaacid andalpha-naphthylamtn, with R-salt as end component-Dissolve aboutthirty-eight parts of the coloring-matter obtained according to thefirst part of this example, taking this quantity of the actualcoloring-matter, preferably in the form of the paste, undried, in onethousand parts of water, to which twentyfive parts of causticsoda lye(containing thirty-five per cent. Na.OH) have been added. To thesolution add seven parts of sodium nitrite in aqueous solution, and thenwhile stirring run the mixed solution into about fifty-five parts ofhydrochloric acid (containing about thirty per cent. real H. 01) dilutedwith three hundred parts of ice-water. After stirring for about half anhour the production of the diazo compound is usually complete. Itappears as a difficultly-soluble brown-red mass, somewhat soluble inalkalies, yielding a blue solution. Add the diazo compound to a sodaalkaline solution of thirty-five parts of R-salt. The production of thecoloringmatter is complete in a short time. Precipitate with commonsalt, press, and dry. In an analogous manner the disazo coloringmatters,using other middle components and other end components, can be obtained.If a base be used as an end component, such as alpha-naphthylamin orethyl-beta-naphthylamin, it is advisable to combine in weakly acidsolution, and subsequently convert the coloring-matter by treatment withcarbonate of soda into its sodium salt.

My new coloring-matters are generally made in the form of a dark-coloredpowder, are

black dyes, and are characterized by extraordinary coloring power, and,further, possess great fastness against the action of light. On treatingthe shades obtained with them with chromates they give shades whichsatisfy the most severe tests as to fastness, to milling, washing, andto light. They are more particularly characterized by their behavior onreduction either with ammonium sulfid in ammoniacal solution or withzinc-dust in a similar solution. On complete reductionchlor-amido-phenol-sulfo-acid occurs in the reduction products, and canbe recognized,

for instance, by diazotizing it and combining with R salt in alkalinesolution. This test may conveniently be carried out as follows: Thecoloring-matter to be tested is dissolved in a little hot water and alarge excess of ammonia is added. Boil the solution and add a smallquantity of sulfid-of-ammonia solution and boil for along time. Thesolution, which is originally deep blue, changes first to an intensered, and after heating for a long time is only slightly yellow-colored.Cool this solution, acidity with hydrochloric acid, and filter. Thefiltrate thus obtained contains the chlor-amido-phenol-sulfo-acid usedin the manufacture of the dye. This can be recognized,for instance,bydiazotizing with sodium nitrite and combining with R salt in alkalinesolution. This combination takes place slowly on standing in the cold ormore quickly on slightly warming. The coloringmatter obtained isblue-violet, which changes to intense red on treatment with hydrochloricacid.

The coloringmattcr which I desire to claim specifically behaves exactlyas described in the above test, and is further characterized by beingreadily soluble in water, giving a blue solution. The solution insulfuric acid is blue-green.

Now what I claim is- 1. The disazo coloring-matters which can beobtained from ortho-chlor-ortho-amidophenol-para-sulfo-acid and whichyield chloramido-phenol-sulfo-acid on reduction, all substantially asdescribed.

2. The disazo coloring-matter which may be obtained fromortho-chlor-ortho-amidophenol-para-sulfo-acid, alpha-napthylamin asmiddle component, and beta-naphthol-3.6-disulfo-acid (R salt) as endcomponent, which is readily soluble in water giving a blue solution,soluble in sulfuric acid giving a bluegreen solution, and which yieldsortho-chlorortho-amido-phenol-para-sulfo-acid upon reduction, allsubstantially 'as described.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

PAUL J ULIUS.

lVitnesses:

ERNEST F. EHRHARDT, M. H. ISLER.

